壳聚糖基可注射型温度敏感性水凝胶

壳聚糖基可注射型温度敏感性水凝胶是一种pH值中性的,在室温或低于室温时可保持液态,温度达到体温时可凝胶化的材料,有望被广泛应用于药物释放和组织工程领域,作为多肽和蛋白质等生物活性药物的可注射型释放载体或组织修复材料.本文介绍了壳聚糖基可注射型温敏性水凝胶的种类、特性、机制和应用等方面的研究进展.     

新型核壳结构水凝胶的合成与表征

以羟丙基纤维素为模板,在水溶液中合成了不含表面活性剂的聚甲基丙烯酸（PMAA）纳米水凝胶。再以该PMAA纳米水凝胶为模板,合成了具有pH和温度双重敏感的聚甲基丙烯酸/聚N-异丙基丙烯酰胺（PMAA-PNIPA）核壳结构纳米水凝胶。对纳米水凝胶的形态、结构、pH以及温度敏感性的表征结果表明,纳米水凝胶粒径为338.8～407.9 nm,并随交联剂用量的增加而减小,其体积相转变具有良好的pH及温度响应性,这种绿色合成的生物相容性新型核壳结构纳米水凝胶具有极为广泛的应用前景。     

交联型温度/pH双敏水凝胶的设计与制备

刺激响应型水凝胶是其结构和性能随环境条件的变化而发生改变的一类智能高分子材料。由于温度和pH值是生物和化学系统的两个重要因素,也是人体的重要生理指标,因此温度/pH双重响应型水凝胶的制备及其在医药领域的应用研究具有重要的理论和现实意义。论文综述了近年来国内外温度/pH双敏水凝胶的设计与制备方法,并对其制备与应用的发展方向进行展望。     

苯乙烯/马来酸酐共聚物智能水凝胶的制备与性能

合成了苯乙烯/马来酸酐共聚物接枝聚乙二醇400(PEG400)水凝胶.研究了环境pH、温度、离子强度对该凝胶溶涨性能的影响,并对凝胶的动态溶涨行为进行了分析.结果显示该水凝胶对环境pH、温度、离子强度等变化均作出体积相转变响应,表现出了智能高分子凝胶的特性.     

天然高分子电场敏感水凝胶——大豆蛋白/羧甲基壳聚糖体系

通过将大豆蛋白(SPI)和羧甲基壳聚糖(CMCS)进行溶液共混,并加入环氧氯丙烷作为交联剂,成功制备了一种天然高分子两性荷电水凝胶.这种SPI/CMCS水凝胶在电场的作用下可以快速弯向一侧电极,表现出很好的电场敏感性.由于该水凝胶具有两性荷电的特性,因此其在不同pH值的电解质溶液中既可以弯向阳极(当pH6时),也可以弯向阴极(当pH6时).除了pH的变化,其他诸如施加电压的大小以及水凝胶的厚度也会对SPI/CMCS水凝胶在电场中的行为产生影响.相比于先前报道的另外两种天然高分子电场敏感水凝胶,即壳聚糖/羧甲基纤维素水凝胶和壳聚糖/羧甲基壳聚糖水凝胶,SPI/CMCS水凝胶在酸性较强(pH=3～4)以及中性(pH=7)的环境中仍能表现出良好的电场敏感性,拓展了天然高分子电场敏感水凝胶的应用范围.     

明胶-聚异丙基丙烯酰胺水凝胶的pH、温度敏感性

用明胶(Gel)和N 异丙基丙烯酰胺(NIPAM)为原料,制备了Gel/聚异丙基丙烯酰胺(PNIPAM)水凝胶;研究了不同含量的水凝胶的温度、pH敏感性。结果表明:温度对水凝胶pH敏感性的影响取决于水凝胶的组成。明胶含量高的水凝胶,其pH敏感性几乎不受温度的影响;当0.500.90时,pH值几乎不影响水凝胶的温敏性。     

壳聚糖基抗菌水凝胶的应用及研究进展

抗菌生物材料因其能够有效抑制细菌感染而被公认为是重要的抗生素替代品。其中抗菌水凝胶因制备工艺简单,结构多样,具有易负载和可控药物释放性、良好的生物相容性和抗菌性等多种特殊功能而受到越来越多的关注。壳聚糖及其衍生物具有高抗菌性、低毒性、生物相容性和降解性等优点被广泛用作抗菌水凝胶材料。本文根据壳聚糖基抗菌水凝胶的性能和抗菌机理,综述了近年来在固有抗菌水凝胶、光响应性抗菌水凝胶、荧光抗菌水凝胶、负载抗菌药物水凝胶和协同抗菌水凝胶等方面的研究进展,探讨了壳聚糖基抗菌水凝胶目前所面临的挑战,并对其未来发展作了展望。     

无皂种子分散聚合法制备单分散双重响应性微凝胶

以N-异丙基丙烯酰胺及2-乙烯基吡啶为主要单体, 采用无皂种子分散聚合法制备了单分散的、具有温度及pH双重响应性能的核-壳结构微凝胶, 并以扫描电镜及动态激光光散射等手段对微凝胶粒子的结构和性能进行了研究. 溶胀行为研究表明, 微凝胶粒子具有独立的互不干扰的温度及pH敏感性能, 其体积相变温度与纯聚N-异丙基丙烯酰胺(PNIPAM)凝胶基本一致, 说明局部分布的弱电离单体不会对PNIPAM凝胶的体积相变温度造成影响.     

羧甲基纤维素钠/聚(N-异丙基丙烯酰胺)纳米复合水凝胶的制备及结构性能表征

以无机粘土为交联剂制备了具有温度、pH双重敏感特性的羧甲基纤维素钠/聚(N-异丙基丙烯酰胺)/粘土半互穿网络纳米复合水凝胶(CMC/PNIPA/Clay semi-IPN),并通过红外和透射电镜对其结构和形态进行了表征。在酸性(pH=1.2)和20℃条件下,分别研究了温度和不同pH缓冲液对该凝胶溶胀度的影响,测定了复合水凝胶的力学性能。结果表明:水凝胶中的粘土被剥离成单片层,且均匀分散在凝胶网络中,起交联剂的作用,而CMC以线性大分子的形态存在;CMC/PNIPA/Clay具有良好的温度、pH双重敏感特性;凝胶的断裂伸长率>1 000%。     

SiO2-HA/PNIPAm核壳温敏微凝胶的合成及其溶胀性能

以SiO₂纳米颗粒为核,以透明质酸（HA）和聚异丙基丙烯酰胺（PNIPAm）的杂化凝胶（HA/PNIPAm）为壳制备了一系列无机-有机杂化核壳结构单分散微凝胶.该微凝胶具有很好的温度敏感性,其最低临界转变温度（LCST）在34 ℃附近;该微凝胶具有负触变性,且温度高于LCST时负触变性更明显.用动态光散射（DLS）测定了微凝胶颗粒的水动力学粒径随温度的变化关系,实验数据可以用我们早前建立的硬核高分子凝胶分子热力学模型进行关联计算,结果表明只需较少的模型参数就可较好地描述温度响应的核壳结构高分子凝胶的溶胀行为.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.